DE2512934A1 - PROCESS FOR THE PREPARATION OF WATER DISPERSIBLE, STABILIZED REACTION PRODUCTS FROM PROTEIN AND ALKYLENE GLYCOL ALGINATES - Google Patents

Description

The invention relates to the production of water-dispersible, stabilized reaction products from protein and alkylene glycol alginates. These stabilized reaction products are used as food additives or as foam stabilizers useful.

There are several types of gels and gums in food compositions as functional ingredients been used. Such materials act as thickeners, suspending agents, and structural stabilizers.

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One of the gums is algin or alginic acid. Alginic acid is a polymannuronic acid, which comes from seaweed (kelp). It stands alongside other forms as the sodium salt (sodium alginate) and in the form of Alkylene glycol esters available. The alkylene glycol alginates have been used as functional components in food.

Alkylene glycol alginate is an esterification reaction product of some of the carboxylic acid groups or alginic acid and an alkylene oxide, alkylene glycol alginates are in generally available as propylene glycol ester of alginic acid, in which about 30 to about 90% of the carboxyl groups have been esterified with propylene glycol, while the rest Groups are either free or neutralized with a base.

Other than the salts of alginic acid are the alkylene glycol alginates generally not precipitated in acidic solutions as low as pH 2-3. Propylene glycol alginate is used as a safe food additive for thickening, suspending or as a solid stabilizer recognized for acidic foodstuffs such as acidic fruit drinks ^.

Propylene glycol alginates are generally alkaline Systems have not been used because it was believed that alkaline conditions would saponify the ester groups, and a decrease in viscosity.

U.S. Patent 3,5o3,769 discloses that propylene glycol alginate under mild alkaline treatment a product with modified properties, i.e. higher viscosity

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did and provides improved suspension capability. The result can be achieved by forming an acidic solution of propylene glycol alginate alone or in combination with a hydroxyl-containing polymer such as starch, carboxymethyl cellulose, guar gum or polyvinyl alcohol, adding sodium carbonate to increase the pH value to the alkaline side, the Lc
Acetic acid acidifies

Side admits, the solution holds .15 F_Lnuten at 13 C and with

While the product according to the method described in the US patent is an improvement over propylene glycol alginate represents, an even greater improvement in thickening properties is desired.

It is also known that proteins such as gelatin, casein and albumin with propylene glycol alginate under alkaline conditions, i.e. above pH 9.6, to form an insoluble (non-dispersible) product can be reacted. U.S. Patent 3,378,373 (or the corresponding GB-PS 962 483) and GB-PS 987 797 teach that this reaction in photographic processes for hardening of photographic gelatin layers containing silver halide contained, is useful. However, this product is insoluble (non-dispersible) and cannot be considered functional Find food additive application because it is not dispersible in water.

In US Pat. No. 3,4o7,076 it is indicated that a protein of the globulin type with an anionic polyelectrolyte such as Sodium alginate at an acidic pH near the isoelectric Point of the protein (about 4.5) can be implemented. The reaction product is a complex necessary to manufacture of whipped toppings should be useful.

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It is known from US Pat. No. 2,444,241 that proteins can be obtained from cheese whey by increasing the pH of the whey above 7, adding sodium alginate and lowers the pH to the acidic range. With acidification a precipitate forms,

Water-dispersible reaction products of protein however, alkylene glycol alginate are unknown in the art. The object of the invention is to create water-dispersible reaction products from protein and alkylene glycol alginate. Another purpose of the invention is in the creation of water-dispersible stabilized reaction products of protein and alkylene glycol alginate, which have useful functional properties required for such applications as thickeners, suspending agents and structural stabilizers or foam stabilizers for foams are useful for fire fighting.

According to the invention is a process for the preparation of water-dispersible, stabilized reaction products of at least one water-dispersible protein and alkylene glycol alginate, in which one

1) a water dispersible protein and a water dispersed alkylene glycol alginate in one reactive pH above 9.5 for a period of time which is sufficient to produce a reaction mixture obtained which contains a water-dispersible reaction product, the reaction mixture an increase in viscosity of at least 4 times the viscosity of an aqueous mixture of not by

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water-dispersible protein set and unreacted protein Has alkylene glycol alginate, and

2) the pH of the reaction mixture to below seven ceases to form a stabilized reaction product dispersed in water «

The stabilized reaction product according to the invention can be dried with appropriate care and in the form of a dry, water-dispersible material obtained v / earth capable of forming thickened dispersions.

The term "reaction mixture" as used herein denotes the alkaline reacted mixture of protein and alkylene glycol alginate,

The term "reaction product" as used herein refers to the solid in the reaction mixture which formed by the alkaline reaction of protein and alkylene glycol alginate.

The term "stabilized reaction product" as used herein refers to the solid in the reaction mixture, which has been formed by the alkaline reaction of protein and alkylene glycol alginate and which to stop a further reaction, e.g. by neutralizing, treated by acidification of the reaction mixture has been.

As used herein, "water dispersible" means "capable of contributing to the formation of a colloidal solution Mixing with water ". The term" water dispersion "denotes an aqueous colloidal solution

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The term "water-dispersible" is essentially unlimited can be diluted with water. As used herein, the term "dispersible" means that the solid is does not settle out of the liquid when left to stand. This applies to the phrase "water dispersible protein and water dispersible reaction product "to.

There can be water-insoluble reaction products from protein how gelatin and propylene glycol alginate are made. If.such water-insoluble products with water are mixed, no dispersion of the product occurs. Even after prolonged stirring, such water-insoluble ones settle Products.

The reaction products formed by the reaction of alkylene glycol alginate and protein are believed to be polymeric nature. Whether or not these products can be used effectively as functional ingredients depends on the degree of reaction. If the degree of reaction is too great (i.e. the molecular weight is too high) this is it Product of little usefulness as a food ingredient because it is relatively difficult to disperse in water is. If the degree of reaction is too low, it will be dispersible in aqueous systems, but will not provide them desired functional properties.

However, there is some degree of reaction between alkylene glycol alginates and proteins in which a product is formed. which is compatible with an aqueous system and nevertheless delivers the desired functional properties.

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The desired products can be added to and dispersed in water. The products absorb water , swell and form thickened dispersions. The resulting thickened dispersions can be dehydrated and the procedure repeated. As indicated above, this ability to form such dispersions and not settle is defined as "dispersibility". Accordingly, a product having an excessively high degree of reaction can disperse in water. Such a product is defined as "non-dispersible" or insoluble and is outside the scope of the invention.

In contrast, there is swelling and dispersion of the produced by the method according to the invention, water-dispersible, stabilized reaction products take place when water is added. It's closed note that in connection with the stabilized reaction products according to the invention, the term "im substantially dispersible "means that at least 90%, and preferably at least 95% or more and more preferably over 98% by weight of the stabilized reaction product is dispersible and is still within the definition of a product made according to the method of the invention. It has been found that in general some mixture is desirable in which the stabilized reaction product does not readily disperse without some assistance can.

The stabilized reaction products according to the invention tend to have the appearance of egg albumin, clear to gray-white color and vary in consistency. A

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Stir a dispersion of the stabilized reaction product generally results in the entrapment of air bubbles during dispersion, which gives the dispersion a cloudy appearance.

The products according to the invention are dispersible in water stabilized reaction products of protein and alkylene glycol alginate. These products can be like they are formed after stabilization or are formed as a dry product from the aqueous mixture can be obtained after stabilization. The products can be obtained from the aqueous mixture by adding an excess a water-miscible solvent such as acetone, isopropanol or the like can be precipitated. The precipitation can then be separated by filtration and carefully dried at room temperature, as excessive Temperatures over long periods of time can destroy the product. The dried product is one in water dispersible material capable of forming a thickened dispersion. There can also be alternative methods of extraction a dried, water-dispersible material, such as spray or freeze drying, are used. Solvent precipitation can be beneficial, though a higher rate of separation is desired. Spray or However, freeze drying is less likely to affect a protein product.

The dried products are dispersible in water Materials capable of forming thickened dispersions, used as thickeners, emulsifiers and foam stabilizers, particularly in the food field, are useful. These products of the procedure

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according to the invention are also used in non-food areas where foam stabilization or Suspension properties are required.

Suitable alkylene glycol alginates for use in the method according to the invention are made by reaction made of alginic acid with alkylene oxides. These products are from II. Maas in "Alginic Acid and Alginates", SCT Publ. Co., Heidelberg (1959), pages 126 to 13o described The reaction products of alginic acid with 1,2-epoxides are particularly advantageous. Examples of such products include ethylene glycol alginate, trimethylene glycol alginate, propylene glycol alginate (made from 1,2-propylene oxide and alginic acid), butylene glycol alginate (manufactured from 1,2-butylene oxide and alginic acid), isobutylene glycol alginate (made from 1,2-1sobutylene oxide and alginic acid) or pentylene glycol alginate (made from 1,2-pentylene oxide and alginic acid) or the like. The aforementioned esters are also described in Ind. Eng «Chem. 4_3, 2o73 (1951), Propylene glycol alginate or propylene glycol alginate is used in the manufacture of additives for food purposes particularly useful as propylene glycol alginate is generally considered to be safe for use in food is recognized.

The alkylene glycol alginates used in the practical execution useful in accordance with the invention may have varying degrees of esterification, but generally have a degree of esterification of at least 25%. The degree of esterification of these alginates is preferably at least 3o% and is particularly preferably within the range of at least 50% to about 95%, and especially in the range from 80% to about 90% of the carboxyl groups. The rest of the carb

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oxyl group is usually partially neutralized with a base.

Proteins that have been found to be particularly useful in making those dispersible in water Stabilized reaction products according to the invention are proteins that are in water at a temperature of 30 ° C or below are soluble or dispersible. This definition excludes proteins that only exist in water are soluble or dispersible at temperatures above 30 ° C, such as gelatin. The in the method according to the invention Useful proteins include milk proteins such as those derived from whole or skimmed milk and those derived Milk proteins, such as cheese whey, both sour and sweet, from methods of making cheese such as cottage or Cottage cheese, cheddar cheese, mozzarella or similar cheese3, in various forms such as raw whey, dried whey, demineralized whey, concentrated or partially of Lactose-depleted whey protein, such as the material made by the process of U.S. Patent 3,547,9oo is, like sodium caseinate, vegetable protein such as proteins from oilseeds exemplified by soy protein and Soy whey, hydrolyzed vegetable protein, vegetable protein from corn, wheat or barley, fish protein, egg burain, blood protein and a cell protein such as yeast. As long as the protein is dispersible in water at temperatures of 30 ° C or below it is believed useful in practicing the invention.

A single source of protein is not required in connection with the invention. Mixtures of two or more proteins are reacted with the alkylene glycol alginate.

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When the water-dispersible stabilized reaction product is dispersed in water, it has been found that the clarity of the dispersion can vary with the type of protein employed. Albinoid-like protein in general and liolk protein in particular
clearer solutions.

In general, the properties of stabilized reaction products of protein and alkylene glycol alginate vary, which are prepared according to the process of the invention, with the nature of the reactants, the reaction sbe conditions and the composition of the initial mixture of the reactants. The conditions that are necessary to produce stabilized reaction products dispersible in water vary within several Reaction systems. The conditions governing the procedure influence and which have to be regulated are the concentration of the reactants, the weight ratio the reactants (alkylene glycol alginate and protein), the temperature, the time during which the Materials are reacted at an alkaline pH, the pH, the amount of alkali added and the process the addition of alkali.

The process is carried out in an aqueous mixture. The initial concentrations of protein and alkylene glycol alginate for any given protein to alginate ratio must be adjusted so that the reaction occurs between the protein and the alkylene glycol alginate under the reaction conditions when the aqueous Mixture has a reactive alkaline pH. It is

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has been found that when the concentration that is in the Mixture of existing reactants is too low, no reaction occurs when treated with alkali. Conversely, the viscosity of the reaction product can become very rapid can be increased to a point where an insoluble, nondispersible gelatinous type of reaction product is created when the concentration of the reactants is too high for the reaction conditions. In general Protein concentrations of about 0.5 to about 35% by weight, based on the reaction mixture, are suitable.

The concentration of the alkylene glycol alginates is usually for practical handling considerations limited by the mixture of viscous solutions of these compositions. Aqueous mixtures, the etv / a o, 2 to contain about 6 wt .-% of alkylene glycol alginate are useful, Preferably, however, aqueous mixtures are used which contain 0.25 to about 4% by weight of alkylene glycol alginate.

The most suitable concentration of reactants for the method according to the invention will vary for any one given system, but it is generally within a comparatively narrow concentration range.

The weight ratio of protein to alginate useful in the method according to the invention varies from 5o: 1 to 1: 5. Preferably, weight ratios of about 2o: 1 to about 1: 5 and in particular of about 2o: 1 applied to about 1: 3. Most preferred ratio for a whey protein and propylene glycol alginate system is in the range of about Io: 1 to about 1: 3.

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In general, as the protein to alginate ratio changes, the properties of the stabilized will vary Reaction product that is produced. For example, when the ratio of protein to alginate increases the viscosity of a dispersion of the stabilized reaction product may decrease. When a stabilized reaction product with a high weight ratio of protein to alkylene glycol alginate by adding one with If a water-miscible solvent, e.g. acetone, is precipitated, the precipitated, stabilized reaction product can be finer divided and difficult to separate and gain.

The temperature at which the protein and the alkylene glycol alginate reacted with one another in an aqueous mixture can be from the freezing point of the aqueous mixture the reactants range to 50 ° C, preferably from about 5 ° C to about 25 ° C, and most desirably from 16 to 20 ° C. It has been found that the reaction temperature employed is related to the concentration of the reactants. An increase in the reaction temperature seeks reaction between reactants at low concentrations, i.e., about 1% or less inhibit. At higher concentrations of proteins, i.e. 5 to 10%, with a 1: 1 ratio of protein to alginate, you can however, temperatures of 35 to 4o C are effectively used. Lowering the temperature of the aqueous mixture of reactants produces a beneficial effect extending the desired reaction, particularly to aqueous mixtures of reactants with protein concentrations less than about IS. At temperatures in the area. from 0 ° to lo ° C, reaction products can be found in water

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are dispersible, are formed from mixtures containing 0.5% by weight of protein. Accordingly, temperatures of the freezing point of the aqueous mixture of reactants up to a temperature up to about 5o C used here are provided, depending on the limiting effects of concentration, as described above is.

The first stage of the process according to the invention requires the reaction of an aqueous mixture of a protein with an alkylene glycol alginate at a reactive pH of approximately approximately 9.5. There are different procedures for Achievement of this result. The protein and the alkylene glycol alginate can be mixed together in an aqueous mixture and rapidly adding sufficient alkali to bring the pH of the entire mixture into the reaction range bring to. In a similar way one can prepare an aqueous mixture of the alkali with protein and one Add sufficient alkylene glycol alginate solution to the mixture provided care is taken is to avoid inadmissible damage to the protein by the alkali. Aqueous solutions of protein, alkylene glycol alginate and alkali can be brought together simultaneously to form the reaction mixture.

Since the alkylene glycol alginate hydrolyzes easily under alkaline conditions, working practices should be avoided we'rden in which the alkylene glycol alginate in contact with the alkali under conditions which are not sufficient for the reaction are to let. One such set of conditions may be a mixture of alkylene glycol alginate with alkali and after standing the material to protein

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admit. It has also been determined to be a slow one Adding alkali to a mixture of protein and alkylene glycol alginate to hydrolyze the alkylene glycol alginate instead of allowing the alkylene glycol alginate to react with the protein. For this reason too, the Addition done quickly.

Generally the minimum reactive pH is approximately 9.5. It has been found that the optimal reactive pH value between 9.5 and about 11.5 depending varies on the type of protein, the concentration, the ratio of reactants and the temperature. Most Reactions within the preferred concentration ranges occur at a pH between about Io and 11 and preferably between lo, 2 and. lo, 8 a. Higher pH values within the preferred range seek the speed with which a thickened reaction mixture is formed. The term "reactive pH" as used herein denotes a pH value at which a reaction product is formed for a particular reaction mixture.

The aqueous mixture of reactants is made convenient by using a sufficient amount of alkali brought into an alkaline state. Alkali is defined for the purposes of the invention as alkali carbonates and hydroxides. Preferred types of alkali are sodium carbonate and sodium hydroxide, potassium carbonate / potassium hydroxide and mixtures of which in the form of an aqueous solution,

In general, the use of a carbonate is opposed A hydroxide is preferred because the hydroxide can locally cause a high pH before a full mix can be reached. The localization of a high pH

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can partially destroy the alkylene glycol alginate.

Ira operation of the procedure it is necessary to the amount of the amount of alkali required to determine the pH of the aqueous mixture of unreacted protein and Bring unreacted alkylene glycol alginate to the reactive pH value above 9.5. For most protein systems a reactive pH within the range of lo.2 to lo.8 has generally been found to be most effective proven. The amount of alkali that is required to a small measured portion of the aqueous mixture of unreacted protein and unreacted alkylene glycol alginate Bringing to a pH in the range of lo.2 to lo.8 is determined separately. The required amount Alkali is then proportional to the amount of the aqueous mixture of reactants to be reacted chosen.

Small adjustments can be made to the amount of alkali to get the optimal pH for any other protein, a certain concentration of reactant, temperature, and a particular protein to achieve alkylene glycol ratio in the mixture. In general, higher pH will provide within the range a faster response.

The amount of alkali that is required to make the aqueous mixture of reactants to the required level Bringing pH four depends primarily on the particular protein, on its concentration in the aqueous mixture addicted.

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Furthermore, the amount of alkali required for the addition varies to the aqueous. Mixing of reactants is needed, something with different systems, in general however, this amount is slightly above the amount required to produce soft or thickened dispersions to create. If amounts of alkali are below that which is required to make the aqueous mixture of reactants To bring to the reactive pH, are applied, occurs .no thickening of the aqueous mixture of reactants a,

For an isolated whey protein propylene glycol alginate system the pH is generally increased to at least 9.5 before the thickening reaction occurs. Preferably the reaction is carried out at a pH value between lo.2 and Io.8

Once the amount of alkali that is required to make the aqueous mixture of reactants to the To bring the required pH, has been determined, the procedure can be carried out by taking the protein and introducing the alkylene glycol alginate and the alkali together into an aqueous mixture.

In carrying out the method according to the invention, it is desirable that the two reactants in the aqueous mixture only brought together at a high enough pH to carry out the reaction. Since that Alkali glycol alginate is easily hydrolyzed by alkali, a slow addition of alkali destroys the alkylene glycol alginate, so that the alkylene glycol alginate does not react

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with protein, at a reactive pH above 9.5 is available. Rapid addition of the alkali to the aqueous mixture of reactants of protein and alkylene glycol alginate generally avoids this hydrolysis problem. Other procedures, wLe rapid Mixing all of the ingredients in one mixing head can also overcome the problem.

After the thickened reaction mixture is formed under alkaline conditions, the reaction must necessarily be carried out by neutralizing the system to a pH below approximately 7 v / earth ended, since the reaction took so long goes on as long as alkaline conditions are maintained. Failure to neutralize the Reaction mixture while the reaction product is still in an aqueous, dispersible state, can either lead to the formation of a product that is no longer dispersible in water (i.e. a water-insoluble one Material) or the reaction product is destroyed and forms a liquid of low viscosity. The stabilization the reaction product is brought about by terminating the reaction, usually by neutralization. One Neutralization is carried out very simply by diluting the reaction mixture with water and then with acid added to the reaction mixture to adjust the pH to below seven. Preferably, the reaction mixture is before the Acidification dilutes so that a rapid homogeneous neutralization is achieved. Acidification and dilution can be carried out simultaneously if a sufficiently dilute acid is used for neutralization.

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The length of time during which the aqueous mixture of reactants did not set at an alkaline pH is also a factor that can affect the property of the product obtained. The response time can therefore be defined as that period of time in which the aqueous mixture of protein and alkylene glycol alginate is maintained at a reactive pH above 9.5 prior to neutralization of the mixture. In practice there is generally a time lag between the increase in pH and the onset of thickening. The delay time depends on the type and concentration of the reactants, the temperature and the pH value.

Response times as short as several seconds to as long as 20 minutes have been observed. However, it is preferred adjust the pH, the concentration, the protein to alginate ratio and the temperature so that Response times of about 15 seconds to 20 minutes and in particular from 30 seconds to 5 minutes are provided. However, it must be taken into account that the response time for a given system of all variables, of pH, concentrations and specific reactants, which are given above is dependent. This time can easily be with a minimum for any given system can be determined from experimental work.

During the reaction, the viscosity of the reaction mixture increases to a maximum and then slowly decreases, when the further reaction occurs. As indicated above, the decrease in viscosity is believed to be one Deterioration or degradation of the product under the alkaline conditions of the reaction.

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If a neutralization and an acidification before the Onset of thickening or after the occurrence of an expanded one As degradation takes place, the resulting dispersible product has a low viscosity when in Water is dispersed.

The reaction product is preferably stabilized by acidifying the reaction mixture _f after the viscosity of the reaction mixture _{t has} increased to at least about 4 times the viscosity of an aqueous mixture of unreacted protein and unreacted alkylene glycol alginate, measured by a Brookfield viscometer, _o Preferably the viscosity of the unreacted aqueous mixture increases the viscosity of the aqueous Reaktionsmischiang measured with a BrookfieId viscometer, by more than 5 to 5oo times before neutralization _s whether "also looo-fold increases in viscosity are well been observed .

It will be appreciated that the term viscosity increase, which is used herein to an increase in the viscosity refers g the wirdj caused .by reacting the protein with the Alkyleiiglykolalginat, and not only to the protein thickening caused by the increase of pH Certain native proteins in aqueous dispersions show increases in viscosity when the pH value is increased. This increase in viscosity is reversible in that it can return to its original state when the pH is lowered.

At high protein concentrations and low protein weight ratios of alkylene glycol alginate, the

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Reaction product that forms, increasing non-dispersible, when the reaction time is increased at the reactive pH. When the amount of non-dispersible material becomes essential, the reaction product loses its functionality. Under these conditions it is necessary » reduce the pH of the reaction mixture below 7 (to neutralize) before a

substantial amount of nondispersible material appears in the reaction product. When you get the reaction product is allowed to remain at the reactive pK value for a period of several hours, the reaction product will be its lose its original thickening properties and transform into a liquid of low viscosity. The liquid of low viscosity is miscible with water, but it has its thickening effectiveness and usefulness lost in the context of the invention.

For these reasons, the maximum duration of the reaction time is that which allows the reaction mixture maintains useful functional properties.

For a 1: 1 system. of whey protein: propylene glycol alginate it has been found that a reaction time of Io to 15 minutes is suitable. In general, the aim is to form a Reaction mixture with maximum viscosity a reaction time of about 30 seconds to 5 minutes are allowed before neutralization by acidification of the reaction mixture (stabilization of the reaction product) takes place. the exact response time for any given system can easily be determined by one skilled in the art.

It is essential that the pH of the reaction mixture be adjusted to below about 7 in order for the reaction to occur

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and to prevent deterioration of the reaction product (stabilization). The pH becomes ordinary not set below about 3 as extremely low pH affects the properties of the stabilized reaction product can affect.

Suitable acids for the acidification stage are hydrochloric acid, Acetic acid, citric acid, sulfuric acid, phosphoric acid or the like, Other acids may also be suitable depending, of course, on the ultimate application of the product, food grade acids are used in the manufacture of food grade products preferred.

The reaction between the protein and alkylene glycol alginate is terminated when the pH of the reaction mixture is adjusted to below 7. The final pH to which the Adjusting the reaction mixture is important in determining the dispersibility of the stabilized reaction product after drying, the acidification pH, which provides optimal dispersibility, varies with the particular system and is usually between 3 and 7. For example, for a reaction mixture with a 1: 1 ratio of whey protein: propylene glycol alginate if sodium carbonate was used as alkali, the pH is generally within the range of about 3.5 to β, ο and preferably set to about 4.5.

It is contemplated that the neutralized reaction mixture by methods known in the art such as filtering, contacting with activated carbon or the like can be treated to improve the color or clarity of the stabilized reaction product.

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The stabilized reaction product can be used as it is or from the aqueous, neutralized one Reaction mixture can be obtained.

Means such as solvent precipitation or Vacuum drying, as has been found, to obtain a dry " A dispersible product capable of forming a thickened dispersion as further described above is suitable is.

While the Annelderin does not go through this explanation desires to bind, the reaction mechanism between the protein and the alkylene glycol alginate is believed to be a nucleophilic one Attack of the amino group present in the rest of the protein on the ester carbonyl group of the alkylene glycol alginate, to be attributed to being amide compounds between the KoIekülverbindungen are formed. It can be assumed that the chemical modification of a protein with alginate residues involves binding which allow formation of the product "The invention is not, however, intended to be based on any particular theory be limited as the exact theory or mechanism by which the product is formed is not known with certainty and the above statements are only intended to facilitate understanding of the invention. Other Theories may explain the phenomenon as well or better.

The invention also includes a water-dispersible reaction product of a water-dispersible protein and an alkylene glycol alginate and a dry water-dispersible one A reaction product of a water-dispersible protein and an alkylene glycol alginate which is capable of to form a thickened dispersion when mixed with water.

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Heating an aqueous dispersion causes additional thickening if the concentration of the reaction product is high enough in the dispersion. A 1% concentration of a reaction product with a 1: 1 weight ratio of alcoholic protein: propylene glycol alginate can be thickened by this treatment. Reaction products made from mixtures with a higher weight ratio of protein: alkylene glycol alginate require higher concentrations in order to achieve an increase in viscosity by heating. If the concentration of the dispersion material is too low, the viscosity will be lowered. The heating of an aqueous dispersion of a stabilized reaction product to a temperature in the range of 75 ° C to about 100 ° C

and preferably to about So ⁰ C is usually sufficient to bring about the change in viscosity. It can be seen that the thickening effect due to heating can be observed in conjunction with the stabilized reaction mixture itself or with dispersions of dried, stabilized reaction product.

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Example i

Production of a stabilized reaction product from whey protein and ProDylen ^ lykolalgir.at in: ratio 1; 1

15.75 g propylene glycol alginate (dry weight) with a degree of esterification of 835a and !! / RE! ("Llanucol Lster", available "from Alginate Industries, Ltd., 22 Henrietta Street, London, England) were dissolved in" water and resulted 1 4-00 g of an aqueous Ki se hung with a propylene glycol alginate concentration of 1.125 wt. 5 &. 29.17 g one in trade available, modified milk protein with a content from £ 54 whey protein, 27p lactose and 3/3 moisture ("EISPHO 50" available from Stauffer Chemical Company, V / estport, Connecticut, V.St.A.) were dissolved in 370.8 g ", / water, 400 g of an aqueous mixture with a protein concentration of 3.94% by weight were obtained.

The two Ilischungen were thoroughly mixed until homogeneous, the temperature was adjusted to 19 ± 0.5 ⁰ C, to obtain an I-Iischung, which was composed of 0.875 / 0.875 ^ llolkeprotein and / »propylene glycol alginate.

With rapid stirring, 72.9 ml of a mono-molar iatriocarbonate solution were added to the protein and ester digestion and after 1 minute the mixture thickened. After a further 4 minutes, the thickened reaction mixture was diluted with 1,800 g v / water, and the mixture was stirred until it was "homogeneous. The excess of alkali was then neutralized with 2N hydrochloric acid about 10 minutes after the addition of alkali. "Now. To lower the ρΐί - .. 'ert to 4.5, about 72 ml of 2N hydrochloric acid were required.

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The reaction product was recovered by pouring the acidified reaction mixture into about 5 vol acetone. The precipitate was allowed to harden, separated by filtration, pressed, washed with several fresh portions Acetone; then it was "dried at room temperature, and..." a solid with a dry ash content of 80-90 ° was obtained.

A sample of this material was added to water and a dispersion resulted with a concentration of Vj> (on a dry weight basis); the slurry was mechanically agitated until dispersion was complete. The resulting thickened dispersion had a pH value of about 5-3 and a viscosity of about 3500 cp, which was measured on a visconeter (Brookfield LVT, 60 rpm, spindle 4, temperature 20 ° C.).

liach heating to 90 ⁰ C, this dispersion was cooled to 20 C, and the result was a further increase in viscosity of the dispersion.

Example 2

Production of a stabilized reaction product from whey protein and Prcovleng lycola lginate in a ratio of 2: 1

The procedure of Example 1 was repeated, with 300 g of an aqueous solution with a content of 0.67 $ propylene glycol alginate (Llanucol Ester 3 / RK, as in Example 1 defined), based on dry moisture, and 1,335j Whey protein (ElIRPRO 50 from Example 1) were used. 15 ml of 2N sodium carbonate solution were added with stirring. laugh to 10 min, the resulting thickened reaction mixture was with

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250 g Y / ater -diluted and to a pH-V / ert of 4.5 with acidified about 16.5 ml of 2N hydrochloric acid. The acidified reaction mixture was then made up to 600 g with water, and there was a reaction product having a concentration of 1 wt .- ^.

Example 3

Manufacture of a stabilized reaction product from whey protein and ProOylengl; / ~ alginate in a ratio of 5: 1

The procedure of Examples 1 and 2 was carried out using an aqueous mixture (300g) containing 0.458> ί propylene glycol alginate (lianucol ester S / RK, as defined in Example 1) based on the dry matter and 2.29% i-Iolkeprotein (EIIRPRO 50 as in Example 1), repeated. 21.7 ml of 2-n ITatriumcarbonatlösung were added with stirring, iiach 5 were added to 10 min 25 ml of water and the reaction mixture to a pH of 5.0 ^T ./ert with about 24 ml of 2N hydrochloric acid.

The acidified reaction mixture was then washed with water made up to 412.5 g and the result was a reaction product having a concentration of 2.0

Examples 4 to U

The general procedures of the examples were followed 1 to 5 followed. Table I gives details on the reactants and other reaction conditions for Examples 1-11.

In each case, the protein and propylene glycol

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alginate dissolved separately, the mixtures were then mixed and an aqueous mixture of the K-reaction participants with the desired composition was obtained. The temperature of the aqueous mixture of reactants was then adjusted to 19 ± 0.5 ° C. Me appropriate amount of alkali v / urde added to adjust the pH ^T .7ert under efficient stirring 2UR preventing a local Snttehens of excessively high pH to increase above 9.5. The reaction mixture thickened to at least four times the viscosity of the aqueous solution of unreacted protein and unreacted alkylene glycol alginate. The reaction mixture obtained was diluted with an amount of water approximately equal to its own weight acidified to the pH value given in Table I with the appropriate length of acid.

The reaction product was precipitated "by the acidified The reaction mixture was poured into acetone; the precipitate was collected, washed with a solvent and dried at room temperature.

The proteins used, given in Table I. are listed below with precise details of their actual protein content (based on dry matter).

modified whey solids 54 $ protein, 2?> £ lactose, EHRPRO 50 $ 3 lbs. Moisture

(Stauffer Chemical Co,)

"Arkasoy 50 Soy Isolate" "50 ^ Protein, in V.'asser at

a natural pH value of 6j5 (i $ ige solution) insoluble (British Arkady Go, ₉ Ltd.)

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ITodium caseinate $ 77 protein, $ 9 moisture

(Laing national)

EialTDumin 75 ^ protein

! Single cell protein

(Yeast product from trials) $ 82 protein

In Table I, the protein concentration refers to the actual amount of protein in the mixture and not to the!.! close to protein-containing material. The propylene glycol alginate concentration is also based on dry matter.

The propylene glycol alginates used in Table I * were obtained from Alginate Industries, London and had degrees of esterification and percentages based on the dry pesticides, as indicated in the following:

* (P.G.A.)

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iPropylene glycol alginate (P.G.A.)

Degree of esterification

Dry pesticides

Viscosity ep

Oi
O
CO i

- “J
co

Manucol Ester Ε / ΕΚ
Manucol Ester E / RE
Manuool Ester E / PL
Manucol Ester M.

83 84 75 60

83

87 86 83

120 100 200 400

Note: Viscosity was measured on a Brookfield L.V.I'-Viscometer measured at 60 rpm "

The temperature was 20 C and a 1% solution was used, with the exception of "when using the Manucol Ester E / HE, where a 2% solution was used ₀

Table I.

For protein protein PGAPGA example conc $> type conc.

Ver Vol. 2 Anäh. Vol.pH value viscosity (cp) holds n-NaCl hydrochloric acid / the reac reaction product nis solution 100 g reaction mix in aq. Protein / 100 g mixed foods

0 .875 E / RK 0 .875 •
• - :1 . · Reaction—
mixture
(ml) mod. Mo Ike-,
solids 1 .33 E / RK 0 .67 1 :1 4.1 mod.MoIke-,
solids 2 .29 E / RK 0 .458 2 :1 5.0 mod. whey,
solids 1. .33 E / RE 0 .67 5 :1 7.2 mod. whey,
solids 2, .292 E / RE 0, .458 2 :1 6.7 mod whey
solids 0. 875 E / PL 0. , 875 5; il 11.7 : mod. whey
solids 0, 875 M. 0. 875 Ij 1 6.50 mod. whey
solids 0. 625 E / RE 0. 625 1: 1 6.67 Sodium-
caseinat 0. 75 E / RE 0. 75 1: 1 3.33 Single
protein 1: 3.33

after arrival
Acidification

Concentration viscosity

et 2 to

4.2

5.5

8.0

7.0

11.9

6.40

6.56

3.33

2.9

4.5

4.5

5.0

4.5

5.0

4.5

4.5

4.5

4.5

1 2

1
.- 1

3650

2100

800

1200

420

(1000) **

2900 (4400) **

4040 (3700) **

2760

1330 (3900) **

Table I.

Examples Protein Protein PG * A "PGA encryption Vol. 2 Annäh. VoI ₀ pH value viscosity (cp)

Conc »? 6 Type Conc · # holds- n-Ha01 ~ hydrochloric acid / the reac ·? · Reaction product

nis solution 100g reaction mixture in aqueous dispers.

Protein / 100 g mixture mixture

ι P _n GJU Reactions- (ml) after An Station ^Vislcosita1! mixture acidification ^

(ml) ' ⁱ

10 soy 1.5 U / RE 1.5 111 5.0 4.6 4.5 2 320 protein (460)

(Arkasoy 50)

S ^ ^{1 egg 1} »75 U / RE 1.75 1: 1 4.84 3.83 4.5 2 690 00

o EmPRO 50 ^

0 f ^

^ · Ϊ> 1β viscosities (Brookfield) were found at the specified concentrations and at

^ 20 C observed for the listed compositions, including Examples 1 through

The values given in brackets indicate the viscosities after heating and Cooling the solution and represent typical increases in this treatment.

1 CjD GO

The reaction products prepared in Examples 1 to 11 were / ater dispersed in V, and it was found DAT, the viscosities of the dispersions according to the protein used varied _o EO showed the reaction products with a ratio of protein: Ester 1: 1, in which Scour or liatrium oaseinate were used, which by far had the highest viscosities, while the reaction product of soy protein had the lowest viscosity, although the reason for this is in part due to the high proportion of insoluble components present in the soy protein. In almost every case, the viscosity increased further after the dispersions of the reaction products were heated to 90 ° C, possibly as a result of the partial denaturation of the protein.

Example 12

Production of a stabilized realization solution Wolk protein and Proyalenglyko! Alginat in a ratio of 10: 1

This became the procedure of the previous examples followed.

300 g of an aqueous solution with a content of $ 0.5 (1 »5 g) propylene glycol alginate (E / RK Hanucol Ester, as in Example 1 defines) and $ 5 (15 g) whey protein (27.78 g EHRPRO 50, as defined in Example 1) were made alkaline with 47 ml of a 2N lithium carbonate solution. ITach 5 to 10 min the resulting thickened reaction mixture was diluted with water and the pH was raised with 2N hydrochloric acid set under 7; a thickened, stabilized dispersion of the reaction product resulted

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- 34 Example 13

Producing a stabilized reaction zone Whey protein and pro ^ / lenglycol alginate in a ratio of 50: 1

The procedure of the previous examples was followed.

300 g of an aqueous solution from reactants, the $ 0.3 (0.9 g) propylene glycol! alginate (E / RK Manucol Ester, as defined in Example 1) on a dry matter basis and 155 * (45 g) whey protein (83.3 g ZiIRPRO 50, as in example 1 defined), were nit 18 ml of 2N sodium hydroxide alkalized. After 5 to 10 minutes, the thickened reaction mixture was diluted with water as required, and the pH was adjusted to below 7 with 2N hydrochloric acid; a thickened, highly viscous dispersion of the reaction product was obtained.

Example 14

Effect of the amount of alkali on the formation of the reaction product

Ewei 200 ml samples of aqueous mixtures of reactants containing 1.25 wt .- ^ propylene glycol alginate with a degree of esterification of about 83 ^ and 1.25 wt .-% whey protein. (2KRPR0 50, as defined in Example 1) were prepared. The viscosity of the mixtures was 35 cp _? as measured using a Brookfield viscometer ο

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17 ml of one-molar sodium carbonate and 23 μl of 7 / water were added to the first sample in about 5 seconds. The final pH- ^{T of} the solutions was 10.7. The viscosity of the alkaline solution was 30 cp after 2 minutes no thickening of the reaction mixture was observed.

To the second sample, 40 ml of one molar sodium carbonate was added over a period of about 5 seconds. The resulting pH-7. ^{The r} ert was about 10.9 »and the viscosity was greater than 500 cp after 2 minutes. Thickening of the reaction mixture was observed. The reaction temperature was 2O ⁰ C.

This example is to be used as a comparison with Example 1 too consider and shows the influence that variations in the type of participants have on the reaction product.

Example 15

Effect of the alkali addition rate on the formation of the functional product

To a 200 ml sample of propylene glycol alginate and whey protein, prepared as in Example 14 above, a total of 40 nl one molar sodium carbonate was added in successive small steps over a period of 5 minutes. The final pE value was 10.9 · The viscosity was 30 ep two minutes after the end of the carbonate addition. E ¹ S no thickening of the pL mixture was observed. The sermeratur of the reaction was 20 ⁰ G.

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Example 16

Effect of reactant concentration on the formation of the reaction product

Two aqueous propylene glycol alginate / whey protein mixtures Of reactants were, as described in the example, with a content of the following amounts of reactants manufactured:

Ee act i ο nsrai s c hung

P.G.A. ■ 1.25 wt. $ 1.5 wt. $

Whey protein 1.25 wt .- $ 1.5 wt .- ^

Either of the two aqueous mixtures of reactants 17 ml of a one molar ilatriuncarbonate solution were added added in 5 seconds. The following results were obtained:

Initial reaction viscosity pH-Tvert final viscosity mixture

A (1.25 / 0 "35 cp 10.7 30 cp B ($ 1.5 42 cp 10.6 500 cp

At a reactant ratio of 1: 1 and a concentration of 1.255 no thickening of the reaction mixture was observed, "however, at a reactant ratio of 1: 1 and a concentration of 1.5%, thickening of the reaction mixture occurred. The temperature of the reaction mixture was 20 ⁰ C «

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Example 17

Effect on the formation of the reaction product when alkali first becomes ^ e ^ to the protein

A 100 nl mixture of 1.6? $ Propylene ^ / colalginate, as defined in example 1, and a 100 nl mixture of 1.6 ml of whey protein (2! TiIPEO 50, - as defined in example 1) manufactured. 20 nl of a one-violet sodium carbonate solution were added to the whey protein mixture. ! laugh About 5 seconds this alkalized milk protein solution became the Propylene glycol alginate solution added. ITaoh 5 see entered Thicken the reaction mixture.

The above example was repeated, but the alkalized whey protein mixture was allowed to stand for 15 minutes before it was added to the propylene glycol alginate solution. No increase in viscosity (no reaction) was observed. The seaction temperatures of both examples were 2O ⁰ G.

Example 18 Formation of the reaction product at elevated temperature

A 5% propylene glycol alginate ester mixture (Ξ / ΕΕ Manucol Ester - low viscosity as defined in Example 4) was mixed with a 10% EHRPR0-50-I mixture (as defined in Example 1 (about 5 % Ifolkeprotein) to form a mixture with a weight ratio of alginate: protein of 1: 1. The viscosity of the mixture before the reaction was 215 ep. Sufficient sodium carbonate solution was added to bring the pH to a range from 10 to 11. The reaction temperature was 40 ⁰ G.

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- 58 -

The viscosity of the "alkaline reaction mixture" was 4,800 cp. After the reaction mixture had been diluted with an equal amount of water, the reaction mixture was neutralized with acid, and a mixture with a viscosity of 6,200 cp resulted. The reaction product was precipitated with acetone and with Haessen carefully dried. The reaction product reused in water at a concentration of 2% gave a dispersion with a viscosity of 1 500 cp. The dried reaction product contained 31 ° protein, based on kg edahl nitrogen, and 14% moisture.

Example 19

Formation of the reaction product with increased r. !Temperature·

A 7% aqueous whey protein mixture (145 * EHRPRO. 50, as defined in Example 1) was with a 7 / ^ igen aqueous Propylene glycol alginate mixture (S / ilS Manucol Ester, as defined in example 4) mixed to make a deletion Reactants with a weight ratio of protein:

1: 1 propylene glycol alginate. The viscosity of the reactant mixture prior to the reaction was. 380 cp. After the. When pH was increased to the range 10-11 with an I sodium carbonate solution, the mixture thickened to a viscosity of 5,000 cp. The üeaktionstemperatur was 5O ⁰ C. The thickened Reaktionsnischung v / urde with an equal amount of V / ater therein contained diluted acid having a sufficiently large Lienge to adjust the pH value to neutrlisieren below. 7 The viscosity of the neutralized reaction mixture was 2,300 cp.

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The reaction product was separated off by precipitation with acetone and dried. Possibly due to an error in the precipitation method, a 2% solution of the reaction product in v / water yielded a composition with a viscosity of 115 cp. The dried reaction product contained $ 35 protein, based on Kgedahl ¹ see nitrogen, and $ 16 moisture.

Example 20

Formation of the reaction product "at lower temperatures (5 ⁰ O)

A 1.0 sequence of wood protein mixture (about 2.0 $ SHRPRO 50, as defined in Example 1) is added with a 1, above propylene glycol alginate mixture (e / RE Llanucol Ester, as defined in Example 4) with a weight ratio of 1: 1 of protein Alginate mixed. The viscosity before the reaction "was 22 ep. A sufficient amount of lithium carbonate solution was added to raise the pH to a range from 10 to 11. The reaction temperature was 5 ° C. after which the reaction mixture settled had thickened, the viscosity of the reaction mixture formed was 4,200 ep. The reaction mixture was diluted with an equal amount of water to give a dilute reaction mixture with a viscosity of 400 cp, after neutralization of the diluted reaction mixture with acid, the viscosity of the neutralized reaction mixture 500 was cp. the ^xi Saf ions product was precipitated with acetone and dried.! laughing redispersion in water at a concentration of 2 $ formed a thickened dispersion having a viscosity of 1240 cp.

509840/0 792

using the following components of the preceding examples "was obtained at a [temperature of 2O ⁰ G Reaktionsnischungen using the procedure:

a) Weight ratio of whey protein to propylene glycol alginate of 1: 5 (0.5% whey protein solution: 2.5% propylene glycol alginate solution);

Td) skimmed milk as a protein source;

c) Propylene glycol alginate with a degree of esterification of

The above mixtures all thickened under alkaline. Bed:
separated.

see conditions "at 20 ⁰ C. The products were not

Example. 21

Formation of the reaction product when using liquid whey

A liquid whey estimated to have a protein content of $ 0.7 was mixed with enough propylene glycol alginate (E / KB Manucol Ester, as defined in Example 4) to provide 1,4 ^ propylene glycol alginates in the liquid whey, referring to this' ./eise a mixture of Reäktionsteilnehmern having a weight ratio of 1: 2 yielded from protein to propylene glycol alginate at 1O ⁰ C. The viscosity before the reaction was 83 cp _o After the alkalization with sodium carbonate to a pH Yiert 10-11, the viscosity rose to 44,000 cp. The reaction mixture formed in this way was diluted with an equal amount of water / volume,

5 0 9 8 U 0 / Q 1 9 2

25Ί2934

and a dilute reaction mixture resulted with a viscosity of 3,000 cp. After neutralization with acid to a pH of less than 7, the viscosity was 900 cp. The product was isolated by the addition of acetone and dried to a moisture content of $ 13. A 2 ° /> ± ge reestablished dispersion yielded a thickened dispersion with a viscosity of 3,800 cp.

Example 22

Application of freeze drying for isolation dos Reaction product

50 ml of a 1; propylene glycol alginate mixture were prepared by dissolving 0.5 g of propylene glycol alginate (E / HE Kanne oil ester, degree of esterification of 85.77%, as defined in Example 4) in 50 ml v / water. 2.5 g of EHRPRO 50, as defined in Example 1, (about 1.25 g of violet protein) were added to this mixture, and the mixture was allowed to come to a reaction temperature of 18 ° C. 7.5 ml of a 2N sodium carbonate solution were then added with stirring to bring the pH to about 10.3. After 55 seconds, 25 ml of Y / ater was added to the thickened reaction mixture that formed. After 5 seconds, the diluted reaction mixture was neutralized (acidified) by adding 8.5 ml of 2N hydrochloric acid with stirring.

The pH of the acidified reaction mixture was raised to checked a pH hetero; it was 6.0. A fraction of the Reaction mixture dispersed in water. The remainder of the sample was freeze dried overnight. The freeze-dried Product could be redispersed in water

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Example 23

g of the alkaline reaction time of the dispersibility of the He ac tion product it in Y. ^r ater

To see if the response time is below alkaline Conditions had any effect on the properties of the final product obtained were as follows Comparative tests carried out at 55 seconds, 2, 4 and 6 minutes.

50ml samples of a 1'iigen Propylenglykolalginatnischung were (as defined E / HE Manucol ester, 85j7 ^c ß> Verßsterunggrad, in Example 4) by dissolving 0.5 g of propylene glycol prepared in 50 nl water. "To this mixture, 5 g EI] EPSO 50, as defined in Example 1 ', was added (about 2.5 g of whey protein), and the mixture of the fractionated liners was allowed to rise to a heating temperature of 18 G

15 ml of a 2 N sodium carbonate solution were then added Stir added to adjust pH to about 10.3. A thickened reaction mixture formed in less than 1 minute. After a period of 55 seconds, 2, 4 and for 6 minutes, the thickened reaction mixture was added with 32 ml of water and 17 ml of 2N hydrochloric acid while stirring neutralized. The pH-Y / er of the acidified mixtures was checked on a pH meter and it was below 7. following Results were obtained:

S09840 / 0792

sample

reaction time

55 see

2 min

4 min

min

Time of ' 30 - 60 see Occurrence of 5.85 ■ thickening Yes pH final value Dispersibility

30 see

4.6

no

40 seo

under 7

no

- 40 see
4.6

no

in water

A portion of the reaction product of Sample A was freeze-dried overnight. The freeze-dried sample was also generally dispersible.

Example 24 Use of potassium carbonate as an alkali

50 ml of a 1% propylene glycol alginate mixture were prepared by dissolving 0.5 g of propylene glycol alginate (L '/ RU Uanucol Ester, 85.7% degree of varesterification, as defined in Example 4) in 50 ml of water. 1.5 g of EHRPHO 50, as defined in Example 1 (about 0.75 g of whey protein) were added to this solution, and the mixture of the reactants was allowed to come to a reaction temperature ^{of 18 ° C.} Then, with stirring, 9 ml of an aqueous 2-n

Potassium carbonate solution was added to bring the pH to about Set 10.3, 30 ml of water were added to the laughing 45 sec added to the thickened reaction mixture that resulted. After a further 5 seconds, the diluted reaction mixture became neutralized (acidified) by adding 9 ml of 2N hydrochloric acid with stirring. The pH value of the acidified reaction mixture was measured on a pH meter; it was below 7. The reaction mixture was dispersible in water.

Example 25

Effect of the alkaline reaction time on the dispersibility of the reaction mixture in water

50 ml of a 1% propylene glycol alginate mixture were prepared by dissolving 0.5 g of propylene glycol alginate (E / RE Manttcol ester, degree of esterification of $ 85.7, as in Example 4 defined) in 50 mJ. water. This vision

5 g EERPRO 50, as defined in Example 1 (2.5 g Idolkeprotein), the mixture of reactants was placed in a water bath and allowed to a reaction temperature of 40 ⁰ C increase. Then 15 ml of 2N ITatriuEic ar b onate solution were added

.509840 / 0792

added with stirring to the pH-Y.'ert to about 10.3 "bring. After 35 see, the" thickened reaction mixture, which resulted, 32 ml ϊ / ater added. After further In this way the dilution of the reaction was carried out Addition of 17 ml of 2N hydrochloric acid neutralized with stirring (acidified). The pH of the acidified mixture was checked on a pH meter; it was below 7 · The neutralized The reaction mixture was dispersible in water.

A similar experiment was carried out under all of the conditions described above, with the exception that the alkaline reaction is 50 seconds instead of 55 seconds as was persevered in the initial attempt. This sample, which was allowed to react longer, was insoluble and not dispersible in water.

For example, 26

Use of a reaction product from oil protein and Propylene glycol alginate in a ratio of 1; 1 in one Salad dressing

It was made a salad dressing using a stabilized Reaction product from whey protein and propylene glycol alginate in a ratio of 1: 1 according to Example 1 as an emulsion stabilizer instead of a propylene glycol alginate stabilizer manufactured using the following components:

S09840 / Ö792

(a) Iq (b) ' jo (ο)

salt 2.5 2.5 2.5 Condiments 0.4 0.4 0.4 sugar 9.7 9.7 9.45 mustard 0.8 0.8 0.8 Colorants 0.1 0.1 0.1 dried egg yolks 1 ^ 35 1.35 . 1.35 10biger vinegar 18.0 18.0 18.0 Wheat oil 27.0 27.0 27.0 stabilized Protein-P.G-.A.- Reaction product 0 ₃ 5 0.5 - Propylene glycol alginate - - 0.5 strength 4.5 4.5 4.5 Ilolke protein - - 0.5 water 35 ^ 15 35.15 34.90

100.00 100.00 100.00

I. Procedure for the preparation of the compositions A and 0

1. Dry blending the sugar, mustard, salt, condiments, starch, and coloring agent and seeing into that Water and the vinegar 'until a homogeneous mixture is obtained,

2. Heat the mixture to 80 to 85 ⁰ G and hold at this temperature for 10 minutes in order to gel the starch.

3 "cooling to 30 ⁰ G or below and adding 3/4 of the oil in the form of a fine stream" stirring at high speed to form an emulsion,

509840/0792

4. Disperse the egg yolk and protein P.G.A. reaction product or the P.G.A. in the rest of the oil and Addition to the solution described above.

5. Homogenize at 119 kg / cm (1,700 psi) to obtain a stable emulsion. This robe was stored ^{at 20 ° C.}

II. Method of Making Composition B

1 · -priorly dissolve the protein P.G.A. product in the water of the composition, addition of the dry ingredients, as indicated in step 1 of method I.

2. Execution of steps 2, 3, 4 and 5 of procedure I. (with the exception that no protein P.G.A. product in step 4 is added).

The following results were obtained:

sample A. B. 0 method I. II I. consistency smooth smooth smooth pourable pourable pourable Viscosity cp 7,000 9 400 10 200

The stabilized reaction product was found to be effective for stabilizing oil emulsions in salad dressings.

The Y / ater dispersible reaction products prepared according to the method of the present £ z .indung can be used as thickening, emulsifying, foam or binder used.

5 0 9 8 4 0/0792

Claims (1)

(a) a mixture of protein dispersible in water at a temperature below 50 ° C and alkylene glycol alginate dispersed in water at a reactive pH sufficiently above 9 * 5 for a sufficient Reacts time period in order to obtain a reaction mixture containing a V / water dispersible reaction product, wherein the reaction mixture has a viscosity increase of at least four times the viscosity of an aqueous mixture of unreacted water-dispersible protein and unreacted alkylene glycol alginate, and (b) adjusts the pH of the reaction mixture below 7, creating a stabilized reaction product of protein and an alkylene glycol alginate dispersed in water. 2. The method according to claim 1, characterized in that the alkylene glycol alginate from the group of ethylene glycol alginate, Trimethylene glycol alginate, propylene glycol alginate, Butylene glycol alginate, isobutylene glycol alginate, pentylene glycol alginate and mixtures thereof. 509840/0792 5. The method according to claim 1 or 2, characterized in that that the protein in a weight ratio to the alkylene glycol alginate in the range of about 50: 1 to about 1: 5 *, preferably from about 20: 1 to about 1: 3, is used. 4. The method according to any one of claims 1 to 3> * thereby characterized in that the reactive pH is within the range of 9 * 5 to about 11.5 *, preferably from about 10 to about 11 and especially from about 10.2 to about 10.8. 5. The method according to any one of claims 1 to 4, characterized characterized in that the reaction temperature at a reactive pH value above 9> 5 within the freezing point range of the aqueous mixture of reactants to about : for example from about 16 ° C to about 20 ° C. 50 ° C, preferably from about 5 ° - to about 25 ° C and in particular 6. The method according to any one of claims 1 to 5 * characterized in that the reaction time at the reactive pH is in the range of about 15 seconds to about 20 minutes, preferably from about 350 seconds to about 5 minutes. 7 · Method according to one of the. Claims 1 to 6, thereby characterized in that the pH of the reaction mixture of step (a) is within the range of about J5 to about 7 * preferably about 5 * 5 to about 5.5. 8. The method according to any one of claims 1 to 7 * characterized in that the reaction mixture from step (a) is diluted with water before the pH is below a value 7 as required in step (b) is set. 509840/0792 - 5ο - 9. Water-dispersible reaction product of a protein and an alkylene glycol alginate. 10, a process for the preparation of a reaction product from whey protein and propylene glycol alginate, characterized in » that the reaction products are dispersible in water, and that one (a) a mixture of whey protein and propylene glycol alginate in water dispersed at a reactive pH sufficiently above 9 * 5 and below about 11 reacts for a period of time sufficient to obtain a water-dispersible reaction mixture, the protein in a weight ratio to the propylene glycol alginate within the range of about 20 § 1 to about 1: 3 and in a concentration of about 0.5 wt. % to about 35 Gevi. ~ #, and the propylene glycol alginate in an amount of about 0.2 wt. ^ to about 6 wt .- ^, based in each case on the total weight of the mixture of the reactants whey protein, propylene glycol alginate and the water in which the two above materials are mixed, is used, the water-dispersible reaction mixture having a viscosity increase of at least that Has four times the viscosity of an aqueous mixture of the unreacted whey protein and the unreacted propylene glycol alginate, and (b) the pH of the reaction mixture within the Adjusts the range from about 3.5 to about 5.5, whereby a obtained stabilized reaction product dispersed in water will. 5Q384Ö / Ö792